Substituted pyrazolines for use as pesticides

Abstract

The present invention relates to novel substituted pyrazolines of formula (I) in which R 1 , R 2 , R 3 and R 4 are as defined in the disclosure, to a plurality of processes for preparing these compounds and their use for controlling pests, and also to novel intermediates and processes for their preparation.

1 - 14 . (canceled)  
     
     
         15 . A substituted pyrazoline of formula (I)  
       
         
           
           
               
               
           
         
       
       or isomers or isomer mixtures thereof,  
       in which 
 R 1  represents halogen or cyano,  
 R 2  represents halogen, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, or cyano,  
 R 3  represents optionally substituted aryl or optionally substituted hetaryl, and  
 R 4  represents hydrogen, cyanomethyl, or alkoxycarbonyl.  
 
     
     
         16 . A substituted pyrazoline of formula (I) as claimed in  claim 15  in which 
 R 1  represents fluorine, chlorine, bromine, iodine, or cyano,    R 2  represents fluorine, chlorine, bromine, iodine, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -alkylthio, C 1 -C 4 -haloalkylthio, C 1 -C 4 -alkylsulfonyl, C 1 -C 4 -haloalkylsulfinyl, C 1 -C 4 -haloalkylsulfonyl, or cyano,    R 3  represents aryl that is optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen, alkyl, alkoxy, alkylthio, alkylsulfonyl, haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfonyl and cyano; represents optionally monosubstituted oxadiazolyl or thiadiazolyl, wherein the substituent is optionally substituted alkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted aryl, or optionally substituted arylalkyl; or represents optionally monosubstituted tetrazolyl, wherein the substituent is optionally substituted alkyl, optionally substituted alkylthio or alkylsulfonyl, optionally substituted aryl or arylalkyl, or optionally substituted cycloalkyl, and    R 4  represents hydrogen, cyanomethyl or C 1 -C 4 -alkoxycarbonyl.    
     
     
         17 . A substituted pyrazoline of formula (I) as claimed in  claim 15  in which 
 R 1  represents chlorine, bromine, iodine, or cyano,    R 2  represents fluorine, chlorine, bromine, iodine, cyano, C 1 -C 2 -alkylthio, or C 1 -C 2 -alkylsulfonyl; or represents C 1 -C 2 -haloalkyl, C 1 -C 2 -haloalkoxy, C 1 -C 2 -haloalkylthio, or C 1 -C 2 -haloalkylsulfonyl having in each case 1 to 5 identical or different halogen atoms selected from the group consisting of fluorine, chlorine, and bromine,    R 3  represents phenyl that is optionally mono- to trisubstituted by identical or different substituents, wherein the substituents are fluorine, chlorine, bromine, iodine, cyano, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio, C 1 -C 4 -alkylsulfonyl, or C 1  -C 4 -haloalkyl, C 1 -C 4 -haloalkoxy, C 1 -C 4 -haloalkylthio, or C 1 -C 4 -haloalkylsulfonyl having in each case 1 to 5 identical or different halogen atoms selected from the group consisting of fluorine, chlorine, and bromine; represents optionally monosubstituted oxadiazolyl or thiadiazolyl, wherein the substituents are 4-alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -alkylthio, or C 1 -C 4 -haloalkylthio; represents phenyl or benzyl, each of which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of halogen, C 1 -C 4 -haloalkyl, and C 1 -C 4  haloalkoxy; represents optionally substituted tetrazolyl, wherein the substituents are C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkylthio, C 1 -C 4 -alkylsulfonyl; represents phenyl or benzyl, each of which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of halogen, C 1 -C 4 -haloalkyl, and C 1 -C 4 -haloalkoxy; or represents cyclopentyl or cyclohexyl, each of which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of C 1 -C 4 -alkyl, and    R 4  represents hydrogen, cyanomethyl or C 1 -C 4 -alkoxycarbonyl.    
     
     
         18 . A substituted pyrazoline of formula (I) as claimed in  claim 15  in which 
 R 1  represents chlorine, bromine, or cyano,    R 2  represents fluorine, chlorine, bromine, iodine, methylthio, trifluoromethyl, trifluoromethoxy, or trifluoromethylthio,    R 3  represents phenyl that is optionally mono- to trisubstituted by identical or different substituents, wherein the substituents are fluorine, chlorine, bromine, iodine, cyano, methyl, methoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio or trifluoromethylsulfonyl; represents an oxadiazolyl group selected from the group consisting of                          where X 1 , X 2 , and X 3  independently of one another represent hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkylthio, or C 1  -C 4 -haloalkylthio; or phenyl or benzyl, each of which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of halogen, C 1 -C 2 -haloalkyl, and C 1  -C 2 -haloalkoxy having in each case 1 to 3 identical or different halogen atoms selected from the group consisting of fluorine, chlorine, and bromine; or represents a tetrazolyl group selected from the group consisting of:                          where X 4 , X 5 , X 6 , and X 7  independently of one another represent hydrogen, C 1 -C 4 -alkyl, C 1 -C 2 -haloalkyl having 1 to 3 identical or different halogen atoms selected from the group consisting of fluorine, chlorine, and bromine; C 1 -C 4 -alkylthio; C 1 -C 4 -alkylsulfonyl; phenyl or benzyl, each of which is optionally mono- to trisubstituted by identical or different substituents selected from the group consisting of halogen, C 1 -C 2 -haloalkyl, and C 1 -C 2 -haloalkoxy having in each case 1 to 3 identical or different halogen atoms selected from the group consisting of fluorine, chlorine; and bromine; or cyclopentyl or cyclohexyl, each of which is optionally mono- to trisubstituted by C 1 -C 4 -alkyl, and R 4  represents hydrogen, cyanomethyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, or n-, i-, s-, or t-butoxycarbonyl.    
     
     
         19 . A substituted pyrazoline of formula (I) as claimed in  claim 15  in which 
 R 1  represents chlorine or cyano,    R 2  represents fluorine, chlorine, bromine, iodine, or trifluoromethylthio,    R 3  represents phenyl that is optionally mono- or disubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, trifluoromethyl, trifluoromethoxy, and trifluoromethylthio; represents an oxadiazolyl group selected from the group consisting of:                          where X 1 , X 2  and X 3  independently of one another represent hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s-, or t-butyl, trifluoromethyl, trifluoromethoxy, or trifluoromethylthio; or phenyl or benzyl, each of which is optionally mono- or disubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, trifluoromethyl, and trifluoromethoxy; represents a tetrazolyl group selected from the group consisting of:                          where X 4 , X 5 , X 6  and X 7  independently of one another represent hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s-, or t-butyl, fluoromethyl, difluoromethyl, trifluoromethyl, 1,1-difluoroethyl, 2,2,2-trifluoroethyl, methylthio, ethylthio, methylsulfonyl, or ethylsulfonyl; phenyl or benzyl, each of which is optionally mono- to disubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, methyl, methoxy, trifluoromethyl, and trifluoromethoxy; or cyclohexyl that is optionally mono- to disubstituted by methyl, and    R 4  represents hydrogen or cyanomethyl.    
     
     
         20 . A substituted pyrazoline of formula (I) as claimed in  claim 15  in which R 1  is cyano.  
     
     
         21 . A substituted pyrazoline of formula (I) as claimed in  claim 15  in which R 2  is halogen.  
     
     
         22 . A substituted pyrazoline of formula (I) as claimed in  claim 15  in which R 2  is fluorine, chlorine, bromine, or iodine.  
     
     
         23 . A substituted pyrazoline of formula (I) as claimed in  claim 15  in which R 1  is cyano and R 2  is chlorine.  
     
     
         24 . A substituted pyrazoline of formula (I) as claimed in  claim 15  in which R 4  is hydrogen or cyanomethyl.  
     
     
         25 . A process for preparing substituted pyrazolines of formula (I) as claimed in  claim 15  comprising 
 (a) reacting a pyrazoline of formula (II)                          or isomers or isomer mixtures thereof,    in which R 1  and R 2  are as defined for formula (I) in  claim 15 , with an isocyanate of formula (III)                          or isomers or isomer mixtures thereof,    in which R 3  is as defined for formula (I) in  claim 15 ,    optionally in the presence of a diluent and optionally in the presence of a catalyst,    to form a pyrazoline derivative of formula (la) according to the invention                          or isomers or isomer mixtures thereof,    in which R 1 , R 2 , and R 3  are as defined for formula (I) in  claim 15 , and, optionally,    (b) reacting the pyrazoline derivative of formula (Ia) with a halide of formula (IV)     Hal 1 -R 4   (IV)   or isomers or isomer mixtures thereof,    in which    R 4  is as defined for formula (I) in  claim 15 , and    Hal 1  represents halogen,    optionally in the presence of a diluent and optionally in the presence of a base;    or    (c) initially reacting an aniline of formula (V)                          or isomers or isomer mixtures thereof,    in which R 3  and R 4  are as defined for formula (I) in  claim 15 , with phosgene in the presence of a diluent and optionally in the presence of a base,    to form a carbamoyl chloride of formula (VI)                          or isomers or isomer mixtures thereof,    in which R 3  and R 4  are as defined for formula (I) in  claim 15 , and reacting the carbamoyl chloride of formula (VI), directly or after intermediate isolation, with a pyrazoline of formula (II)                          or isomers or isomer mixtures thereof,    in which R 1  and R 2  are as defined for formula (I) in  claim 15 , in the presence of a diluent and optionally in the presence of a base.    
     
     
         26 . A pesticide comprising one or more compounds of formula (I) as claimed in  claim 15  and one or more extenders and/or surfactants.  
     
     
         27 . A method of controlling pests comprising allowing an effective amount of a compound of formula (I) as claimed in  claim 15  to act on pests and/or their habitat.  
     
     
         28 . A process for preparing a pesticide comprising mixing a compound of formula (I) as claimed in  claim 15  with one or more extenders and/or surfactants.